JPS6136870B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention comprises a 2,2'-alkylene-bisphenol compound and/or a thiodi (fatty acid alkyl ester) compound, and a compound of the formula () [In formula (), R ¹ and R ² are the same or different and are a halogen atom, an alkyl group, a cycloalkyl group,
It represents an allyl group, an aralkyl group, an alkaryl group, and a cyano group, and m and n represent 0 and an integer of 1 to 4. ] The present invention relates to a stabilized organic polymer composition containing a cyclic organophosphorus compound represented by the following. Conventionally, various stabilizers have been added to organic polymeric substances, especially synthetic or semi-synthetic resins, depending on their use, and in many cases, proposals have been made to achieve their effects by complementary combinations of each stabilizer. It is also being implemented. Among these stabilizers, the most commonly used and effectively used are so-called low molecular weight hindered phenol compounds. Among them, 2,6-di-tertiary butyl-4-cresol (BHT) is particularly common.
This substance has an excellent stabilizing effect on organic polymeric substances, but because it has a large sublimation property near its melting point (69°C) and at temperatures above it, it is difficult to heat-process polymeric substances to which it is added. It has the disadvantage that it loses its effectiveness due to volatilization. To compensate for the shortcomings of such low molecular weight hindered phenol stabilizers, low polycondensates of tertiary alkyl group-introduced compounds such as phenols and cresols and formaldehyde, etc., have been proposed. Among these, 2,2'-alkylene-bisphere type compounds are phenolic stabilizers, but they become colored just by adding them to polymeric substances and heating and mixing them, or if the heating time is too long, they become oxidized to metals, etc. It has the property that coloring progresses markedly even though there is no contact with it. The contaminating nature of this so-called stabilizer is a serious drawback depending on the intended use of the added polymeric substance. Also, sulfur-based stabilizers include thiodi (fatty acid alkyl ester) compounds, such as dilauryl-thio-
Similar staining properties are observed when using dipropionate, which limits its use regardless of its effectiveness. The inventors of the present invention have arrived at the present invention as a result of various studies on how to use these stabilizers without impairing their original effects and eliminating their staining properties. In other words, 2,2′-alkylene-
By adding together a bisphenol compound and/or a thio-bis (fatty acid alkyester) compound and a cyclic organophosphorus compound represented by the above formula (), contamination can be eliminated and the inherent stabilization of each can be achieved. An organic polymer composition having a synergistic effect between the effect and the stabilizing effect of the compound represented by formula () can be obtained. Specifically as the compound of the above formula, for example,
9,10-dihydro-9-phosphor-10-oxaphenanthrene-9-oxide (HCA, Sanko Kagaku
Co., Ltd. (trade name), (hereinafter only the substituents on the diphenyl skeleton will be described) 1-chloro (or bromo, fluoro), 1,3-dichlor (or dibrome, difluoro), 1,3,7-trichlor (or tribrome) , trifluoro), 1-methyl, 1,3-dimethyl, 1,3,7-trimethyl, 3-t-butyl, 1-cyclohexyl, 3-(α-methylbenzyl), 1-phenyl, 3-phenyl, 1 -(4-methylpheni), 3-cyano, 1-methyl-3-chlor (or brome), 1-methyl-3,7-dichlor (or dibrome), 1,3,7-trimethyl-2,6-dichlor (or dibrome), 1-phenyl-3-chlor (or brome), 1-chloro (or bromo)-3-benzyl, 1-chloro-3-brome, 1,3-dibromo-7-chlor, etc. . Organic polymer substances include natural, semi-synthetic, and synthetic polymer substances, especially polyethylene, polypropylene,
Examples include polybutadiene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyamide, polyimide, polycarbonate, polyphenylene oxide, polyurethane, polyphenol resin, polyester, and copolycondensates and mixtures thereof. Contaminating 2,2'-alkylene-bisphenol compounds include 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4- ethyl-6-tertiary butylphenol), 2,2'-methylene-bis(4-methyl-6
-tertiary octylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), 2,2'-methylene-bis{6-(1-methylcyclohexyl)-4-cresol} Illustrated. Contaminant thiodi (fatty acid alkyl ester)
Type compounds include diethyl-thio-dipropionate, dimyristyl-thio-dipropionate, dilauryl-thio-dipropionate, distearyl-thio-dipropionate, lauryl stearyl-thio-
An example is dipropionate. The total amount of stabilizers added is 0.005 to 2 per 100 parts (by weight, the same hereinafter) of the substance to be stabilized.
part, preferably about 0.01 to 1 part. formula()
The amount of the organic phosphorus compound represented by is about 20 to 80%, preferably about 40 to 60% of the total amount of stabilizers. There are no particular restrictions on the method of adding these stabilizers to the organic polymeric substance, but when heating and mixing, at least the stabilizer represented by formula () should be added so that it does not come after the contaminating stabilizer. is preferable. It is of course possible to incorporate stabilizers, fillers, etc. other than those mentioned above. Next, examples of the present invention will be described. Examples 1 to 7 Various stabilizers were added in various proportions per 100 parts of polypropylene (unstabilized product, abbreviated as PP) in a Henschel mixer and thoroughly mixed, and then pelletized with a pelletizer at a cylinder temperature of 20°C. The appearance of the obtained pellets was visually observed, and in some cases, the degree of yellowing (abbreviated as YI) and melt flow index (abbreviated as MFI) were measured. This pellet
Place 10g in a hard glass test tube and heat to 220℃ or 250℃.
After heating for 30 minutes, cool and observe the appearance and YI.
and measured MEI. The test results are also shown in Table 1 as comparative examples for cases where the compound represented by formula () is not used in combination and when other organophosphorus stabilizers are used instead. The abbreviations in Table 1 are as follows. M-1; 2,2'-methylene-bis(4-methyl-
6-tertiary butylphenol) M-2; 2,2'-methylene-bis(4-ethyl-
6-tertiary butylphenol S-1; dilauryl-thio-dipropionate HCA; 9,10-dihydro-9-phosphor-10-
Oxaphenanthrene-9-oxide {In formula (), when m=n=0} P-1; Tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite P- 2; Distearyl pentaerythritol diphosphonite

【table】

[Table] As shown in Table 1, when HCA is used in combination with a staining stabilizer, the staining property can be effectively improved without impairing the physical properties of the polymeric substance to be stabilized. In place of HCA in Examples 1 to 7, 1-cyclohexyl-9,10-dihydro-9-phosphor-10-oxaphenanthrene-9-oxide, 3
-(α-methylbenzyl)-9,10-dihydro-
9-Phosphor-10-Oxaphenanthrene-9-
Similar results were obtained using oxide.

Claims (1)

[Scope of Claims] 1 2,2'-alkylene-bisphenol compound and/or thiodi (fatty acid alkyl ester) compound, and the formula () [In formula (), R ¹ and R ² are the same or different and are a halogen atom, an alkyl group, a cycloalkyl group,
It represents an aryl group, an aralkyl group, an alkaryl group, and a cyano group, and m and n represent 0 and an integer of 1 to 4. ] A stabilized organic polymer composition with improved staining properties, which contains a cyclic organophosphorus compound represented by the following.